Organic compounds containing both sulphur and nitrogen



Patented Jan. 30, 1945 I t I I UNITED STATES PATENT OFFlC-Efy ORGAYIO COMPOUNDS CONTAININGBOTH SULPHUR AND NITROGEN Edward S. Blake, Nitro, W. Va, assignor to Monsanto Chemioal'Company, St. Louis, Mo., a corporation of Delaware I g No Drawing. Application November 7', 19 40,- v

H Serial No. 364,753

9 Claims. (or. 260-241) The present. invention relates to the prepara- Typica-l'texamples of; sulphides which may tion of organic compounds containing both sulemployed inthe present process comprise mr+- v phur and nitrogen. pholine mono sulphide, morpholinc disulp ltler In accordance with thi invention it has been pipericline. mono sulphide, piperidine disulphide, I

found that organic sulphides in which a sulphur piperidine phenyl sulphide, piperidine o-nitro atom is linked directly to a'nitrogen atom form phenyl sulphide, piperidine' p-nitro pheny-l suladditive products with carbon bisulphide or carp idapiperidine ben ot' y su phide, piperidine bon oxysulphide. The productsso produced are chlor benzothiazyl' sulphid p peridine naphtho-t believed to be derivatives of carbamic acids and th-iazyl sulphide; piperidine methyl thiazyl sillmore particularly to contain the group 10 phide, me hylcyclohexy amine' onosulphide; methyl 'cyclohexylamine disulphide, ethyl cyclo- /N- sg hexylamine disulphide, ethyl cyclohexylamine phenyl sulphideethyl cyclohexylamine' behzo thiazyl sulphide, ethyl cyclohexylamine. 4 phe'nyl Where X is oxygen or sulphu Since many higher 5 benzothiazyl sulphide; proply, I cyqmhexylamme.

sulphides are of varying and uncertain composition it has not'been possible to establish the' correctness of this view in all cases. However it amine mono Sulphlde amyl cyclohexylamme d1 seems most probable that the reaction proceeds as sulphlde amylicyclohexylamme benzothlazyl sub methyl benzothiazyl sulphide, butyl cyclohexyl-' 1 follows. f e d yl amine mono: sulph de, diethv v alminefdisulphide and equivalents and analogues ereo a I R+CSX N if Thefollowingare'specificembodiments' ofthe X inventionand-are to be understood'as illustrative where X represents oxygen or sulphur, n repre- 0f t einveu i nsbut in now-ise' limitative-thereof. sents'an' integer and R an organicradical. In Example? this'connectionit'is evident that where R is a t p radical in which nitrogen is linked to sulphur Into S P reactiontvessehfitlledr' h there is opportunity for a second molecule of csX stirrer a r flu condens r th re was cha ed I t i; and as a tt f fact t has been 27 parts by weight of piperidine disulphide (subfound to take place. However, the presence of 3Y ly u a Propo t o s) and 0 one sulphurtonitrogen linkage is sufiicient' t parts-by welght f n d sulp ide- (su stanpermit the above type reaction and R'may be a y y that 0.26 molecular proportion These. i

organic'radical in which carbon is linked to sulactams were brought into s u b he ad phur. Thus, unsymmetricalaswell as symmetrif a suitable i e so ve as for ex p e p cal sulphides/may be reactedwith cs2 0r cos. o l ether the, e stirred until? Without limiting the invention it may be stated reaction was p e vabout u hQ s-b i s'snfl' that sulphides of strong secondary amines react ficient- The i 0h Separatedinitially soon" with ease to produce product of high stability ld fi d'w st -qf nd combined with possessing valuable properties for accelerating the mrther nof milieu-9111 b ained after revulcanization of rubber. A particularly useful 40 moval q hghe prod t'after one reclass of amines for this purpose are secondary crystallization from e e e ted at'l20 l-2l".

amines in which the nitrogen atom is either part a Wa b l e diwyc nentamethylof a saturated heterocyclic ring or is linked to a ene) thluram polysulphldegon' which the" saturated cyclic groupfas for example N alkyl; W was 2 v cyclohexylamines, morpholine, piperidine and the 1, t

like. 'I'hiuramsulphides are produced by action Where c'o'n veni ofcarbon bisulphid'e onthe symmetrical sulphides be reacted with a sulphur-halide to forman'a'mirie of these amines. Accordingly-the present invensulphide and the latterre'acted directly with CS2 tion provides a novel process for the preparation or COS thus eliminating thestep of" isolating the of thiuram sulphides, many of which are widely amine sulphides-Ti er example72parts-by weight used for accelerating the vulcanization of rubber. of 95% piperidine dissolved in asuitable'solvent A particular object of the invention is to provide asfor example petroleum, th w treated with, a novel process for the preparation of thiuram Z'iip'arts by weightl f sulphurrehloride, s

' polysulphides. Other and further objects will be 10vC'.,o'r below. Piperidine hydrochloride-formed hereinafter ho n, g asa by-product in the reaction was demoved, prefen't' or desirable the aminemay erably by filtration and the clear filtrate combined with 40 parts by Weight of carbon disulphide substantially as described in the foregoing example. The overall yield was 89% based on the sulphur chloride.

Example III dried. The product believed to be di(cyclopentamethylene carbamyl) polysulphide melted at 127- 129 C. after one recrystallization from benzene.

Example IV To 116 parts by weight of 98% methyl cyclohexylamine dissolvedin an inert organic solvent there was slowly added at C. or below and with eflicient stirring, 33.75 part by weight of sulphur chloride diluted with an inert solvent. The methyl cyclohexylamine hydrochloride was filtered oil and to the clear filtrate of methyl cyclohexylamine disulphide there was added 50 parts by weight of carbon bisulphide. The resulting mixture was stirred for about hours or until reaction was complete, then the solvent removed and the residue taken up in a mixture of ether and benzene and washed with Water. After removal of the solvent a good yield of a resinous product believed to be dimethyl dicyclohexyl thiuram polysulphide was obtained.

Ewomple V Carbon oxysulphide was passed into a solution of 28.8 parts by weight of N-methyl cyclohexylamine disulphide dissolved in an inert organic i solvent until the gas was no longer absorbed. A small amount of sulphur which had precipitated was filtered off after which the solvent was removed leaving as a residue a viscous amber 011. Since the amount of gas absorbed corresponded to a mol to molreaction the product was believed to be methyl cyclohexyl carbamyl, methyl cyclohexylamine trisulphide.

Example VI Into a suitable reaction vessel there was charged substantially 30.6 parts by weight of morpholine mono sulphide and substantially 750 parts by weight of carbon bisulphide. The charge was heated at refluxing temperature for about 18 hours, then most of the carbon bisulphide removed and the precipitated product filtered therefrom. Substantially 46 parts by weight of a product melting at 149-150 was obtained which product was found to contain 43.9% sulphur and 7.78% nitrogen. The values calculated for di- (morpholyl N thio carbamyl) trisulphide are sulphur 44.9% and nitrogen 7.86%.

The identical product may be obtained from the reaction of morpholine disulphide and carbon bisulphide, one atom of sulphur being split out in the reaction.

. Erample VII 23.6 parts by weight of morpholine disulphide were dissolved in a suitable organic solvent as for benzene and. dried. 29.5 parts by weight or a white crystalline product melting at 179-l81 C. were obtained. Analysis for sulphur and nitrogen indicated that the product was probably a. trisulphide of the probable formula OH2 CH1 era-om o NCSSSCN o CHaC-z g g \CH2-C2 Example VII 1 Substantially 25 parts by weight of piperidine benzothiazy1 sulphide and substantially 25 parts by weight of carbon bisulphide were dissolved in a suitable solvent as for example 200 parts by weight of acetone, and charged into a suitable reaction vessel. The solution was stirred for several hours and allowed to stand for one day after which it was filtered from a precipitate identified as di benzothiazyl disulphide (formed as the result of a side reaction), the solvent removed and the product washed with ether. The foregoing procedure resulted in a light colored crystalline product melting at 96-98 C. which after one recrystallization from petroleum ether was raised to 98-102 C. Analysis for sulphur and nitrogen gave the following results ascomparedto thosecalculated for cyclopentamethylene thiocarbamyl benzothiazyl disulphide.

The principal reaction between carbon bisulphide and cyclopentamethylene amino thio benzothiazole therefore proceeds as follows:

/ CH2-C 2 0.50 part by weight of this product compounded into a rubber stock comprising pale crepe rubber 100 parts, zinc oxide 10 parts, sulphur 3 parts, and stearic acid 0.50 part provided a stock which cured in 60 minutes at the temperature of five pounds steam pressure per square inch and 'possessed a modulus of elasticity of 1075 lbs/in. at 500% elongation and an ultimate tensile of 4830 lbs./in.

The present invention is limited'solely by the claims attached hereto as part of the present specification.

. Whatisclaimed is:

l. The method of making derivatives of carbamic acids by disrupting a nitrogen to sulphur bond. of an organic sulphide and introducing SC=X between the nitrogen and sulphur which consists of treating a sulphide of the structure N-s..R

with SC=X where R represents an organic radi heterocyclic ring, X is selected from a group consisting of oxygen and sulphur and n is an integer less than three.

2. The method of making derivativesof carbamic acids by disrupting a nitrogen to sulphur bond of an organic sulphide and introducing SC=X between the nitrogen and sulphur which consists of treating a sulphide of the structure \CH2 7 with SC=X, X is selected from a group consisting of oxygen and sulphur, n is an integer less than three, the group is the residue of a strong heterocyclic amine and with SC=X, X being selected from a group consisting of oxygen and sulphur and n is an integer less than three and the group is the residue of a strong heterocyclic amine.

phide.

which consists of treating a sulphide possessing the structure with carbon bisulphide, the group CHi is the residue of a strong heterocyclic amine and n being an integer less than three, .both the nitrogen to sulphur bonds being disrupted and each replaced by a nitrogen bond to the carbon atom of different carbon bisulphide molecules.

'7. The method of making di(cyclo.pentamethylene) thiuram polysulphide which consists of treating piperidine disulphide with carbon disul- 8. The method of making di(morpholyl N-thio carbamyl) polysulphide which consists of treating morpholine disulphide with carbon disulphide.

9. The method of making carbamyl sulphides which consists of treating an amine sulphide having at least one sulphur atom linked directly to an amino nitrogen atom with SC=X where X is selected from a group consisting of oxygen and sulphur, the said nitrogen to sulphur bond being disrupted and replaced by a nitrogen bond to the carbon of the CS=X. I

EDWARD S. BLAKE.

4. The method of making thiuram sulphides 

